KR20180035227A - Photocurable resin composition, fuel cell and sealing method - Google Patents

Abstract

An object of the present invention is to provide a photocurable resin composition which is rapidly cured by irradiation with active energy rays such as ultraviolet rays and has excellent adhesion to an electrolyte membrane which is a material which is hard to adhere. Specifically, there is provided a photocurable resin composition containing the following components (A) to (C).
(A): a polymer having a polyisobutylene skeleton containing - [CH ₂ C (CH ₃ ) ₂ ] - units having at least one (meth) acryloyl group,
Component (B): photo radical polymerization initiator,
(C): a silicone oligomer having at least one alkoxy group and at least one (meth) acryloyl group, a silicone oligomer each having at least one alkoxy group and at least one amino group, and a silane compound having at least one isocyanate group One or more compounds

Description

Photocurable resin composition, fuel cell and sealing method

The present invention relates to a photo-curable resin composition which is rapidly cured by irradiation with active energy rays such as ultraviolet rays and has excellent adhesion to an electrolyte membrane which is a material which is difficult to adhere.

Recently, fuel cells have attracted attention as a new energy system for automobiles and households. A fuel cell is a power generation device that extracts electricity by chemically reacting hydrogen and oxygen. In addition, fuel cells are the next generation power generation devices because they are energy efficient at the time of power generation and water is generated by the reaction of hydrogen and oxygen. There are four types of fuel cells: a solid polymer type fuel cell, a phosphoric acid type fuel cell, a molten carbonate type fuel cell and a solid oxide type fuel cell. Among them, the solid polymer type fuel cell has a relatively low operating temperature (about 80 deg. And is expected to be used for a small power source for an electronic device such as an automobile power source, a household electric power generating device, a mobile phone, and an emergency power source.

1, a cell 1 of a solid polymer type fuel cell is an electrolyte membrane electrode assembly 5 (MEA) in which a polymer electrolyte membrane 4 is sandwiched between an air electrode 3a and a fuel electrode 3b, A frame 6 for supporting the MEA, and a separator 2 in which a gas flow path is formed.

In order to start the solid polymer type fuel cell, it is necessary to separately supply the fuel gas containing hydrogen to the anode (anode) electrode and the oxidizing gas including oxygen to the cathode (cathode) electrode separately. If the isolation is insufficient and one gas is mixed with the other gas, the power generation efficiency may be lowered. In this background, sealing agents are widely used for the purpose of preventing leakage of fuel gas, oxygen gas and the like. Specifically, a sealing agent is used between adjacent separators, between the separator and the frame, between the frame and the electrolyte membrane, or between the MEA.

As a sealing agent used in a solid polymer type fuel cell, a hydrogen silylation reaction using a polyisobutylene polymer is preferable because it is a rubber elastomer having excellent gas permeability, low moisture permeability, heat resistance, acid resistance and flexibility. (Refer to Patent Document 1), a thermosetting resin composition (see Patent Document 2) that conducts a hydrocyanation reaction using a fluoropolyether compound (see Patent Document 2), a thermosetting resin (See Patent Document 3), and a heat curable resin composition using an ethylene-propylene-diene rubber (see Patent Document 4) have been examined. However, since the heat-curable resin compositions of Patent Documents 1 to 4 require a heating step for curing, there is a problem that it takes a long time and deterioration of the electrolyte membrane due to heating.

Accordingly, a photo-curing resin composition capable of realizing a process shortening and preventing deterioration of the electrolyte membrane due to heat has been attracting attention. Patent Documents 5 and 6 disclose photo-curable sealants containing polyisobutylene diacrylate, (meth) acrylic monomer, and photoinitiator.

Japanese Patent Application Laid-Open No. 2004-111146 Japanese Laid-Open Patent Publication No. 2004-075824 Japanese Patent Application Laid-Open No. 2007-100099 Japanese Laid-Open Patent Publication No. 2011-124258 Japanese Published Patent Application No. 2009-531516 Japanese Unexamined Patent Application Publication No. 2-88614

However, although the photo-curable resin compositions disclosed in Patent Documents 5 and 6 contain polyisobutylene diacrylate as a main component in order to obtain sealing property, the photo-curable resin composition is insufficient. In addition, although the photo-curing resin compositions disclosed in Patent Documents 5 and 6 contain polyisobutylene diacrylate having low polarity as a main component in order to obtain sealing property, there is a problem that adhesion to various members is inferior due to the structure thereof . Moreover, since the polymer electrolyte membrane of the fuel cell is a fluorine-based polymer, it is extremely difficult to adhere with a conventional sealing material, and further, it is difficult to adhere to the photo-curing resin composition of Patent Documents 5 and 6.

From the above, there is a demand for a photo-curing resin composition that both cures rapidly by irradiation of an active energy ray such as ultraviolet rays and the adhesion to an electrolyte membrane which is a material difficult to adhere.

An object of the present invention is to provide a photo-curable resin composition which is rapidly cured by irradiation of an active energy ray such as ultraviolet rays and has excellent adhesion to an electrolyte membrane which is a material difficult to adhere.

The present invention relates to a photo-curing resin composition characterized by containing the following components (A) to (C).

(A): a polymer having a polyisobutylene skeleton containing - [CH ₂ C (CH ₃ ) ₂ ] - units having at least one (meth) acryloyl group,

Component (B): Photo radical polymerization initiator

(C): a silicone oligomer having at least one alkoxy group and at least one (meth) acryloyl group, a silicone oligomer each having at least one alkoxy group and at least one amino group, and a silane compound (silane coupling agent) having at least one isocyanate group ≪ / RTI >

Further, another aspect of the present invention may be as follows.

[One]

A photocurable resin composition comprising the following components (A) to (C):

(A): a polymer having a polyisobutylene skeleton containing - [CH ₂ C (CH ₃ ) ₂ ] - units having at least one (meth) acryloyl group,

Component (B): Photo radical polymerization initiator

(C): a silicone oligomer having at least one alkoxy group and at least one (meth) acryloyl group, a silicone oligomer each having at least one alkoxy group and at least one amino group, and a silane compound having at least one isocyanate group One or more compounds.

[2]

The photocurable resin composition according to [1], further comprising (meth) acrylate monomer as the component (D).

[3]

The photocurable resin composition according to [2], wherein the component (D) is a (meth) acrylate monomer having an alkyl group having 5 to 30 carbon atoms or an aliphatic cyclic group having 5 to 30 carbon atoms.

[4]

The photocurable resin composition according to any one of [1] to [3], wherein the amount of the component (C) is 0.1 to 30 parts by mass based on 100 parts by mass of the component (A).

[5]

The photocurable resin composition according to any one of [1] to [4], wherein the component (A) is a polymer having a polyisobutylene skeleton represented by the general formula (1).

[Chemical Formula 1]

In the general formula (1), R ¹ represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic hydrocarbon group, and PIB represents a polyisobutylene containing the - [CH ₂ C (CH ₃ ) ₂ ] Butylene skeleton, R ⁴ represents a divalent hydrocarbon group of 2 to 6 carbon atoms which may contain an oxygen atom, R ² and R ³ each independently represent a hydrogen atom and a monovalent hydrocarbon group of 1 to 20 carbon atoms, R ⁵ represents a hydrogen atom, a methyl group, an ethyl group or a propyl group, and n is an integer of 1 to 6;

[6]

(C) is a silicone oligomer having at least one alkoxy group and at least one (meth) acryloyl group, at least one alkoxy group and at least one amino group, respectively, in any one of [1] to [5] , And the kinematic viscosity (kinematic viscosity) of the silicone oligomer at 25 캜 is less than 45 mm ² / s.

[7]

A photo-curable sealant for a fuel cell comprising the photo-curable resin composition according to any one of [1] to [6].

[8]

[7] The photo-curable sealant for a fuel cell according to [7], wherein the photo-curable sealant for a fuel cell is a photo-curable sealant for a peripheral member for a member selected from the group consisting of a separator, frame, electrolyte, fuel electrode, air electrode and electrolyte membrane electrode assembly, , Sealant.

[9]

[7] The method according to [7], wherein the photo-curable sealant for fuel cells is a sealant between adjacent separators in a fuel cell, a sealant between the separator and the frame in the fuel cell, or a sealant between the frame of the fuel cell and the electrolyte membrane or electrolyte membrane electrode assembly Wherein the sealant is a sealant.

[10]

The encapsulant according to any one of [7] to [9], wherein the fuel cell is a solid polymer type fuel cell.

[11]

A cured product obtained by photo-curing a photocurable resin composition according to any one of [1] to [6].

[12]

1. A fuel cell comprising any one of the group consisting of a seal between adjacent separators in a fuel cell, a seal between the separator and the frame in the fuel cell, and a seal between the frame of the fuel cell and the electrolyte membrane or electrolyte membrane electrode assembly, Wherein one of the seals comprises a cured product according to < RTI ID = 0.0 > [11]. ≪ / RTI >

[13]

[12] The fuel cell according to [12], wherein the fuel cell is a solid polymer type fuel cell.

[14]

CLAIMS 1. A method for sealing at least a portion between at least two flanges in a component to be sealed having at least two flanges, characterized in that at least one of the flanges is capable of transmitting light of an active energy ray, A step of applying the photocurable resin composition of any one of the above [1] to [6] to the surface, a step of attaching one flange coated with the photocurable resin composition and the other flange through the photocurable resin composition And a step of irradiating an active energy ray through the light-transmitting flange to cure the photo-curing resin composition to seal at least a part of the region between the at least two flanges.

[15]

A method of sealing at least a portion between at least two flanges in a component to be sealed having at least two flanges, characterized in that a photocurable resin composition according to any one of the above [1] to [6] is applied to at least one flange of the flange A step of applying an active energy ray to the applied photo-curable resin composition to cure the photo-curable resin composition to form a gasket made of a cured product of the photo-curable resin composition, and a step of forming the other flange And a step of sealing at least a part between the at least two flanges by pressing one of the flanges coated with the photo-curable resin composition and the other flange through the gasket, Sealing method.

[16]

A method of sealing at least a portion between at least two flanges in a component to be sealed having at least two flanges, comprising the steps of: disposing a gasket forming mold on at least one flange of the flange; A method for producing a photo-curable resin composition, comprising the steps of: injecting a photo-curable resin composition according to any one of [1] to [6] into at least a part of a gap between flanges in which a mold is placed; Curing the composition to form a gasket made of a cured product of the photo-curing resin composition; separating the mold from the one flange; and placing the other flange on the gasket, The other flange is compressed through the gasket, and the at least two planes Characterized in that it comprises a step for sealing at least a portion between the sealing method.

The present invention provides a photocurable resin composition which is rapidly cured by irradiation of active energy rays such as ultraviolet rays and has excellent adhesion to an electrolyte membrane which is a material difficult to adhere.

1 is a schematic cross-sectional view of a single cell of a fuel cell.
2 is a schematic view showing the entire fuel cell.

Hereinafter, the present invention will be described in detail.

≪ Component (A) >

The component (A) used in the present invention is particularly limited as long as it is a polymer having a polyisobutylene skeleton containing - [CH ₂ C (CH ₃ ) ₂ ] - units having at least one (meth) acryloyl group It is not. As the component (A), for example, - other than the units _{- [CH 2 C (CH 3} ) 2] - unit (polyisobutylene backbone) may _{have, "- [CH 2 C (} CH 3) 2] Other constituent unit ". The component (A) contains, for example, 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more of the - [CH ₂ C (CH ₃ ) ₂ ] By mass or more. Further, the component (A) contains -, [CH ₂ C (CH ₃ ) ₂ ] - units, for example, not more than 100 mass%, and in another embodiment not more than 95 mass% % Or less. (A) preferably has 1 to 6, more preferably 2 to 4, more preferably 2 to 3, particularly preferably 2 (meth) acryloyl groups. The polymer in the present invention is not limited to the theory but can be defined as, for example, a compound having a repeating unit of a monomer in a main chain of the polymer and having a repeating unit of 100 or more.

As the component (A), a polymer having a polyisobutylene skeleton represented by the general formula (1) is preferable from the viewpoint of excellent photo-curability and adhesion to an electrolyte membrane. Specific examples of the component (A) include a polyisobutylene polymer having a (meth) acryloyloxyalkoxyphenyl group. Although the main skeleton of the component (A) of the present invention is a polyisobutylene skeleton, insofar as the effect of the present invention is not impaired, isobutylene is mainly used as the monomer constituting the polyisobutylene skeleton Other monomers can be copolymerized. The component (A) is preferably liquid at room temperature (25 캜) in view of excellent workability.

[Chemical Formula 1]

In the general formula (1), R ¹ represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic hydrocarbon group, preferably a polyvalent aromatic hydrocarbon group, and particularly preferably a phenylene group. PIB represents a polyisobutylene skeleton containing the - [CH ₂ C (CH ₃ ) ₂ ] - units (or consisting of - [CH ₂ C (CH ₃ ) ₂ ] - units. R ⁴ represents a divalent hydrocarbon group of 2 to 6 carbon atoms which may contain an oxygen atom, and is preferably a hydrocarbon group of 2 or 3 carbon atoms. Each of R ² and R ³ independently represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms, preferably a hydrogen atom. R ⁵ represents a hydrogen atom, a methyl group or an ethyl group, preferably a hydrogen atom or a methyl group. n is an integer of 1 to 6, particularly preferably an integer of 2 to 4;

The molecular weight of the component (A) of the present invention is not particularly limited, but from the viewpoint of fluidity and physical properties after curing, the number average molecular weight by chromatography measurement is preferably, for example, 500 to 500,000, 1,000 to 100,000, particularly preferably 3,000 to 50,000. In addition, the number average molecular weight was calculated by standard polystyrene conversion method using size permeation chromatography (SEC).

The viscosity of the component (A) of the present invention at 25 캜 is not particularly limited, but is preferably 5 to 3000 Pa · s, more preferably 50 to 2500 Pa · s , And particularly preferably from 100 to 2,000 Pa · s. The viscosity is preferably 5 Pa · s or more, preferably 50 Pa · s or more, more preferably 100 Pa · s or more, for example, 3000 Pa · s or less, preferably 2500 Pa S or less, and more preferably 2,000 Pa s or less. A particularly preferred viscosity is 1550 Pa · s. Unless otherwise stated, the viscosity was measured by using a cone plate type viscometer at 25 캜.

The method for producing the component (A) is not particularly limited, but known methods can be used. For example, Polymer Bulletin, Vol. 6, pp. 135-141 (1981), T. P. Liao, J. P. Kennedy and Polyer Bulletin, Vol. 20, pp. 253-260 (1988), Puskas et al. And a method of reacting the terminal hydroxyl group-containing polyisobutylene polymer with acrylic chloride or methacryloyl chloride. Examples of the method for producing the other component (A) include a method of reacting a terminal hydroxyl group-containing polyisobutylene polymer with a compound having a (meth) acryloyl group and an isocyanate group, a method of reacting a compound having a terminal hydroxyl group polyisobutylene polymer and an isocyanate group (Meth) acryloyl group with a compound having a hydroxyl group and a method of reacting the terminal hydroxyl group polyisobutylene polymer with (meth) acrylic acid or (meth) acrylic acid lower ester by dehydration esterification or ester exchange And the like.

The method of producing the polyisobutylene polymer represented by the general formula (1) is not particularly limited, but preferably the halogen-terminated polyisobutylene polymer disclosed in Japanese Patent Application Laid-Open No. 2013-216782 and the polyisobutylene polymer represented by the general formula (Meth) acryloyl group and a phenoxy group as represented by the formula (2) shown below. The halogen-terminated polyisobutylene polymer can be obtained by a known method, but can be obtained, for example, by cationic polymerization, and more preferably by living cationic polymerization.

(2)

In the general formula (2), R ² , R ³ , R ⁴ and R ⁵ may be the same as defined in the general formula (1). Specifically, R ⁴ represents a divalent hydrocarbon group which may contain an oxygen atom having 2 to 6 carbon atoms. R ² and R ³ each independently represent a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms. R ⁵ represents a hydrogen atom, a methyl group or an ethyl group. Examples of the compound represented by the general formula (2) include phenoxy methyl acrylate, phenoxy ethyl acrylate, phenoxy propyl acrylate and the like, preferably phenoxy ethyl acrylate.

≪ Component (B) >

The photo-radical polymerization initiator (B) used in the present invention is not limited as long as it is a compound which generates a radical or the like by curing the component (A) of the present invention by irradiating an active energy ray. Herein, the active energy ray includes all of a wide range of light such as radiation such as alpha rays and beta rays, electromagnetic waves such as gamma rays and X rays, electron beams EB, ultraviolet light of about 100 to 400 nm, and visible light of about 400 to 800 nm And preferably ultraviolet rays. Examples of the component (B) include a photopolymerization initiator such as an acetophenone based photo radical polymerization initiator, a benzoin based photo radical polymerization initiator, a benzophenone based photo radical polymerization initiator, a thioxanthone photo radical polymerization initiator, an acylphosphine oxide based photo radical polymerization initiator And a titanocene-based photo-radical polymerization initiator. Of these, from the viewpoint of obtaining a cured product having excellent curability by irradiating an active energy ray, an acetophenone photo radical polymerization initiator, a benzophenone photo radical polymerization initiator, A pin oxide-based photopolymerization initiator is preferable. These may be used alone, or two or more of them may be used in combination.

Examples of the acetophenone photo radical polymerization initiator include, but are not limited to, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzyldimethylketal, 4- Phenyl-ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane- 2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, Oligomers, and the like, but are not limited thereto. IRGACURE 184, IRGACUR 1173, IRGACURE 2959, IRGACURE 127 (manufactured by BASF), and ESACURE KIP-150 (manufactured by Lamberti s.P.A.) can be mentioned as commercial products of the above acetophenone-based photo radical polymerization initiator.

As the benzophenone-based photo radical polymerization initiator, for example, benzophenone may be mentioned.

The acylphosphine oxide-based radical photopolymerization initiator is not particularly limited, and examples thereof include bis (2,4,6-trimethylbenzoyl) -phenyl-phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl - phosphine oxide, and the like, but are not limited thereto. Commercially available products of the acylphosphine oxide-based photo-radical polymerization initiator include IRGACURE TPO, IRGACURE 819 and IRGACURE 819DW (manufactured by BASF).

The blending amount of the component (B) of the present invention is not particularly limited, but is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 20 parts by mass, from the viewpoint of photocurability, relative to 100 parts by mass of the component (A) , Particularly preferably 1 to 15 parts by mass.

≪ Component (C) >

In the present invention, the component (C) comprises a silicone oligomer each having at least one alkoxy group and at least one (meth) acryloyl group, a silicone oligomer each having at least one alkoxy group and at least one amino group, and a silane compound having at least one isocyanate group A coupling agent), and the like. The component (C) of the present invention can be used as an adhesion promoter in the photo-curing reaction. By combining with other components of the present invention, it is possible to achieve adhesion improvement by imparting an adhesive force to a hardly adhesive material .

The silicone oligomer each having at least one alkoxy group and at least one (meth) acryloyl group is preferably a silicone oligomer having at least an alkoxy group and a (meth) acryloyl group in the side chain. Further, the silicone oligomer each having at least one alkoxy group and at least one amino group is preferably a silicone oligomer having at least an alkoxy group and an amino group in the side chain. The component (C) of the present invention is preferable in that it is in a liquid state at 25 占 폚 in that it has excellent adhesion and application workability to the electrolyte membrane. The alkoxy group of the component (C) is not particularly limited, and examples thereof include a methoxy group and an ethoxy group.

Examples of the silane compound having at least one isocyanate group include, but not limited to, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, isocyanatopropyltrimethoxysilane And the like.

The silicone oligomers each having at least one alkoxy group and at least one (meth) acryloyl group, or the silicone oligomers each having at least one alkoxy group and at least one amino group are not particularly limited, but are easily permeable to an electrolyte membrane as a porous material, It is preferable that the kinematic viscosity at 25 캜 is less than 45 mm ² / s, particularly preferably not more than 40 mm ² / s. The kinematic viscosity at 25 캜 is preferably 10 mm ² / s or more, and particularly preferably 20 mm ² / s or more. The silicone oligomers each having at least one alkoxy group and at least one (meth) acryloyl group, or the silicone oligomers each having at least one alkoxy group and at least one amino group are not particularly limited, but from the viewpoint of excellent adhesion to the electrolyte membrane, The amount of the alkoxy group is preferably from 18 wt% to less than 50 wt%, particularly preferably from 19 wt% to less than 35 wt%. The silicone oligomer of the present invention is not particularly limited and includes, for example, compounds having an average molecular weight in the range of 500 to 5,000 and having a structure such as dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, and the like. The silicone oligomer is not particularly limited, but can be obtained by a condensation reaction of an alkoxy group-containing silane compound having an alkoxy group.

KR-513, X-40-2672B (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned as commercially available products of silicone oligomers each having at least one alkoxy group and at least one (meth) acryloyl group in the side chain. Examples of commercially available products of silicone oligomers having one or more amino groups on their side chains include X-40-2651 (manufactured by Shin-Etsu Chemical Co., Ltd.), and commercial products of silane compounds having at least one isocyanate group include KBM-9007, KBE-9007 , KBE-9207 (manufactured by Shin-Etsu Chemical Co., Ltd.), A-1310 and Y-5187 (Momentive Performance Matrix Japan Ltd.).

The blending amount of the component (C) of the present invention is not particularly limited, but is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, particularly preferably 1 to 20 parts by mass, per 100 parts by mass of the component (A) 10 parts by mass. When the component (C) is in the above range, adhesion to the electrolyte membrane is excellent.

≪ Component (D) >

The (meth) acrylate monomer as the component (D) of the present invention is a compound which is polymerized by the type of radicals generated by the component (B) of the present invention. However, the component (A) of the present invention is excluded. As the component (D), for example, monofunctional, bifunctional, trifunctional and multifunctional monomers can be used. Of these, monomers which are compatible with the component (A) (Meth) acrylate monomers having an alkyl group having 5 to 30 carbon atoms or an aliphatic cyclic group having 5 to 30 carbon atoms are preferable from the viewpoint of excellent compatibility. The number of carbon atoms is, for example, 2 or more, preferably 3 or more, more preferably 5 or more, further preferably 7 or more and, for example, 30 or less, preferably 20 or less Preferably 15 or less, more preferably 10 or less.

The (meth) acrylate monomer having an alkyl group having 5 to 30 carbon atoms is not particularly limited, and examples thereof include 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) (Meth) acrylate, dodecyl (meth) acrylate, dodecyl (meth) acrylate, isodecyl (meth) acrylate, lauryl , Nonadecane (meth) acrylate, 3-heptyldecyl-1- (meth) acrylate, stearyl (meth) acrylate and the like. Examples of the (meth) acrylate monomer having an aliphatic cyclic group of 5 to 30 carbon atoms include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) (Meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate and dicyclopentenyl (meth) acrylate. The component (D) Can be used.

The blending amount of the component (D) is not particularly limited, but is preferably 3 to 300 parts by mass, more preferably 5 to 200 parts by mass, and particularly preferably 10 to 100 parts by mass, per 100 parts by mass of the component (A) to be. In this case, if the amount of the component (D) is 3 parts by mass or more, the surface curability is not reduced. If the amount is 300 parts by mass or less, the moisture permeability of the photocurable resin composition is not lowered.

<Optional ingredients>

(Meth) acryloyl group-containing oligomer (not containing the component (A) of the present invention), an thermal radical initiator, a polythiol compound, a tertiary Additives such as fillers, storage stabilizers, antioxidants, light stabilizers, plasticizers, pigments, flame retardants, adhesion-imparting agents, and surfactants can be used.

The oligomer having the (meth) acryloyl group (not including the component (A) of the present invention) is not particularly limited, and examples thereof include a urethane (meth) acrylate having a polybutadiene skeleton, a hydrogenated polybutadiene skeleton Urethane (meth) acrylate of polyester skeleton, urethane (meth) acrylate of polyester skeleton, urethane (meth) acrylate of polyester skeleton, urethane (meth) acrylate of polyester skeleton, urethane (Meth) acrylate, hydrogenated isoprene (meth) acrylate, epoxy (meth) acrylate, and (meth) acrylic group-containing acrylic polymer. Among these, (Meth) acrylate of the polybutadiene skeleton, the urethane (meth) acrylate of the hydrogenated polybutadiene skeleton Urethane (meth) acrylate, urethane (meth) acrylate of castor oil skeleton, isoprene type (meth) acrylate and hydrogenated isoprene type (meth) acrylate.

The thermal radical initiator is not particularly limited, and examples thereof include ketone peroxide, peroxyketal, dialkyl peroxide, hydroperoxide, peroxyester, diacyl peroxide, peroxydicarbonate and the like. These compounds may be used alone or in combination of two or more.

Examples of the polythiol compound include, but are not limited to, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3 Trimethylol ethane tris (3-mercaptobutyrate), trimethylol ethane tris (3-mercaptobutyrate), ethylene glycol bis (3-mercapto glycolate), butanediol bis (3- Mercapto glycolate), trimethylolpropane tris (3-mercaptoglycolate), pentaerythritol tetrakis (3-mercapto glycolate), tris- [(3-mercaptopropionyloxy) (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate, ), Pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) , 3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, and the like. These compounds may be used alone or in combination of two or more.

Examples of commercially available products of the polythiol compounds include TMTP, PETP (manufactured by YODO CHEMICAL CO., LTD.), TEMPIC, TMMP, PEMP, PEMP-II-20P, DPMP (SC Organic Chemicals Co., Ltd.), MTNR1, MTBD1, MTPE1 Ltd.) and the like, but the present invention is not limited thereto. These compounds may be used alone or in combination of two or more.

In the present invention, a tertiary amine compound can be blended for the purpose of improving the photocurability. Examples of the tertiary amine compound include, but are not limited to, trimethylamine, triethylamine, tributylamine, N, N'-diethanolamine, N, N'-dimethyl- N, N'-dimethylamino-acetophenone, N, N'-dimethylaminobenzophenone, N, N'-diethylamino- Benzophenone, triisopropanolamine, and the like.

In the present invention, a styrenic copolymer may be blended for the purpose of adjusting the rubber property of the cured product. Examples of the styrenic copolymer include, but not limited to, styrene-butadiene copolymer, styrene-isoprene copolymer (SIP), styrene-butadiene copolymer (SB), styrene-ethylene-butylene- ), Styrene-isobutylene-styrene copolymer (SIBS), acrylonitrile-styrene copolymer (AS) and styrene-butadiene-acrylonitrile copolymer (ABS).

In the present invention, for the purpose of improving the modulus of elasticity, fluidity and the like of the cured product, fillers can be added to such an extent that the storage stability is not impaired. Specific examples thereof include organic powders, inorganic powders and metal powders. Examples of fillers for the inorganic powder include glass, fumed silica, alumina, mica, ceramics, silicone rubber powder, calcium carbonate, aluminum nitride, carbon powder, kaolin clay, dry clay minerals and dry minerals. The blending amount of the inorganic powder is preferably about 0.1 to 100 parts by mass based on 100 parts by mass of the component (A). When the amount is at least 0.1 part by mass, a sufficient effect can be expected. When the amount is 100 parts by mass or less, the flowability of the photo-curable resin composition can be sufficiently maintained and a constant workability can be maintained.

The fumed silica can be blended for the purpose of adjusting the viscosity of the photo-curing resin composition or improving the mechanical strength of the cured product. Preferably those obtained by subjecting to hydrophobic treatment with organochlorosilanes, polyorganosiloxanes, hexamethyldisilazane, or the like. Specific examples of the fumed silica include commercially available products such as Aerosil R974, R972, R972V, R972CF, R805, R812, R812S, R816, R8200, RY200, RX200, RY200S, .

Examples of the organic powder filler include polyethylene, polypropylene, nylon, crosslinked acrylic, crosslinked polystyrene, polyester, polyvinyl alcohol, polyvinyl butyral and polycarbonate. The blending amount of the organic powder is preferably about 0.1 to 100 parts by mass with respect to 100 parts by mass of the component (A). If it is at least 0.1 part by mass, a sufficient effect can be expected. If it is 100 parts by mass or less, the flowability of the photo-curable resin composition can be sufficiently maintained and workability can be maintained.

Examples of the filler of the metallic powder include gold, platinum, silver, copper, indium, palladium, nickel, alumina, tin, iron, aluminum and stainless steel. The blending amount of the metallic powder is preferably about 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, per 100 parts by mass of the component (A).

In the present invention, a storage stabilizer may be added. Examples of the preservative stabilizer include radical absorbers such as benzoquinone, hydroquinone and hydroquinone monomethyl ether, metal chelating agents such as ethylenediaminetetraacetic acid or its 2-sodium salt, sulfuric acid, acetylacetone and o-aminophenol It is possible.

In the present invention, an antioxidant may be added. Examples of the antioxidant include, for example,? -Naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert- Quinone compounds such as 5-di-tert-butylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone and 2,5-di-tert-butyl-p-benzoquinone; (4-methyl-6-tert-butylphenol), catechol, tert-butylcatechol, 2-butyl-4-hydroxyanisole, 2,6- butyl-p-cresol, 2- [tert-butyl-6- (3-tert- Butylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4'-butylidene-bis (6-tert- , 4,4'-thiobis (6-tert-butyl-3-methylphenol), 3,9-bis [2- [3- (3- Oxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, pentaerythritol tetrakis [3- (3,5- Dihydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl- butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3- (3,5- ) Propionamide] benzene propanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C ₇ -C ₉ branched alkyl esters, 2,4-dimethyl-6- (1-methyl-penta 3,3 ', 3 ", 5,5', 5" - (4-hydroxyphenyl) methyl] phosphonate, (Mesitylene-2,4,6-tolyl) tri-p-cresol, calcium diethylbis [[3,5-bis (1,1-dimethylethyl (4-hydroxyphenyl) methyl] phosphonate, 4,6-bis (octylthiomethyl) -o-cresol, ethylene bis (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris 4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -triene, 1,3,5-tris [ 2, 6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) Reaction of 4,6-trimethylpentene Phenols such as 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, picric acid and citric acid; Tris (2,4-di-tert-butylphenyl) phosphite, tris [2- [[2,4,8,10-tetra-tert- butylbenzo [d, f] [1,3 2] dioxaphosph (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis [2,4-bis (1,1-dimethylethyl) ] Ethyl ester phosphoric acid, tetrakis (2,4-di-tert-butylphenyl) [1,1-bisphenyl] -4,4'-diylbisphosphonite, 6- [3- -4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphepine; Diaryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3- Lauryl thiopropionate), and 2-mercaptobenzimidazole; Amine-based compounds such as phenothiazine; Lactone-based compounds; Vitamin E-based compounds, and the like. Among them, phenol compounds are preferable.

In the present invention, a light stabilizer may be added. Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl- ) Sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert- butyl-4-hydroxyphenyl) propionyl Oxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, Pentamethyl-4-piperidinyl-methacrylate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) [[ (Octyloxy) -4-hydroxyphenyl] methyl] butyl malonate, decane diacid bis (2,2,6,6-tetramethyl- N, N ', N' '' - tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6,6-tetramethyl- -Tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine-N , N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) Poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl- Piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], dimethyl succinate and 4-hydroxy-2,2,6,6 - tetramethyl-1-piperidine ethanol, a polymer of 2,2,4,4-tetramethyl-20- (beta -lauryloxycarbonyl) ethyl-7-oxa-3,20-diazadispyrio [ , 2,2,6,6-tetramethyl-4-piperidyl) -dodecyl ester / tetradecyl ester, N- (2,2,6,6- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7- Oxa-3,20-diazadis pyrrolo [5,1,11,2] heneic acid-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [ 5,1,1, 11,2] -heenic acid-20-propanedododecyl S Bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester, 2,2,2,6,6-tetramethyl- N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) A hindered amine type; Benzophenone compounds such as octabenzone; 4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [ 3- (3,4,5,6-tetrahydrophthalimide-methyl) -5-methylphenyl] benzotriazole, 2- (3- tert- Methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole, methyl 3- (3- (2H-benzotriazol- -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol, and benzotriazole such as 2- (2H-benzotriazole- A sol-based compound; Benzoate-based compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; And triazine-based compounds such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5 - [(hexyl) oxy] phenol. Particularly preferred are hindered amine compounds.

In the present invention, an adhesion-imparting agent may be added. Examples of the adhesion-imparting agent include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 -Acryloxypropyltrimethoxysilane, methacryloxyoxytitrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (? -Methoxyethoxy) silane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Mercaptopropyltrimethoxysilane,? -Aminopropyltri (Aminoethyl) -? - aminopropyltrimethoxysilane, N -? - (aminoethyl) -? - aminopropylmethyldimethoxysilane,? - ureidopropyltriethoxysilane, Hydroxyethyl methacrylate phosphate ester, methacryloxy Hour and the like of ethyl acid phosphate, methacryloxypropyl oxyethyl acid phosphate monoethylamine banyeom (halt salt), 2- hydroxyethyl methacrylate acid phosphate. Of these, hydroxyethyl methacrylate phosphate ester, methacryloxyoxyethyl acid phosphate, methacryloxyoxyethyl acid phosphate monoethylamine salt, and 2-hydroxyethyl methacrylic acid phosphate are preferred. The content of the adhesion-imparting agent is preferably from 0.05 to 30 parts by mass, more preferably from 0.2 to 10 parts by mass, per 100 parts by mass of the component (C).

The photocurable resin composition of the present invention can be produced by a conventionally known method. For example, a predetermined amount of the component (A) to the component (C) and other arbitrary components are mixed and mixed at a temperature of preferably 10 to 70 ° C, more preferably 20 to 50 ° C, Deg.] C, particularly preferably at room temperature (25 [deg.] C) for preferably 0.1 to 5 hours, more preferably 30 minutes to 3 hours, particularly preferably 60 minutes.

<Application Method>

As a method for applying the photocurable resin composition of the present invention to an adherend, a known sealing agent or adhesive method is used. For example, methods such as dispensing, spraying, inkjet, screen printing, gravure printing, dipping, and spin coating using an automatic dispensing apparatus can be used.

<Curing method>

There is no particular limitation on the light source for curing the photo-curable resin composition of the present invention by irradiating with the above-mentioned active energy rays, for example, ultraviolet rays or visible rays. Examples of the light source include low-pressure mercury lamps, A halogen lamp, a xenon lamp, an LED, a fluorescent lamp, a solar light, and an electron beam irradiating device, and the like can be given as examples of the mercury lamp, the high pressure mercury lamp, the ultra high pressure mercury lamp, The irradiation dose of light irradiation is preferably 10 kJ / m ² or more, more preferably 15 kJ / m ² or more in terms of the properties of the cured product.

<Hard goods>

The cured product of the present invention is obtained by curing the photo-curable resin composition of the present invention by irradiating active energy rays such as ultraviolet rays by the curing method. If the cured product of the present invention is one obtained by curing the photo-curable resin composition of the present invention, it is not known what kind of curing method it is.

&Lt; Use and sealant >

The photo-curable resin composition or the cured product of the present invention is preferably used as a photo-curable sealant. The sealing agent of the present invention includes the use of an adhesive, a coating agent, a casting agent, and a potting agent. In addition, when used in this application, the photo-curing resin composition of the present invention is preferably liquid at 25 占 폚.

As a specific use of the sealant, the photo-curable resin composition or the cured product thereof of the present invention is a rubber elastomer excellent in low permeability to air, low moisture permeability, heat resistance, acid resistance and flexibility, A laminate of a battery, a lithium ion battery, an electrolytic capacitor, a liquid crystal display, an organic EL display, an electronic paper, an LED, a hard disk device, a photodiode, an optical communication circuit, an electric wire, a cable and an optical fiber, , Sensors, substrates, medicines, medical instruments, and equipment. Among these applications, the photocurable resin composition of the present invention is particularly preferably used for a fuel cell because it quickly cures by irradiation with active energy rays such as ultraviolet rays and has excellent adhesion to an electrolyte membrane which is a material difficult to adhere.

<Fuel Cell>

A fuel cell is a power generation device that extracts electricity by chemically reacting hydrogen and oxygen. There are four types of fuel cells: a solid polymer type fuel cell, a phosphoric acid type fuel cell, a molten carbonate type fuel cell, and a solid oxide type fuel cell. Among them, a solid polymer type fuel cell has a relatively low operating temperature And electric power generation efficiency, it is used for a small power source and an emergency power source for electronic devices such as a power source for an automobile, a household power generator, a mobile phone, and the like.

1, a cell 1 of a representative solid polymer fuel cell is an electrolyte membrane electrode assembly 5 (MEA) having a structure in which a polymer electrolyte membrane 4 is sandwiched between an air electrode 3a and a fuel electrode 3b. , A frame (6) for supporting the MEA, and a separator (2) in which a gas flow path is formed. Further, at the time of starting the solid polymer type fuel cell, a fuel gas (hydrogen gas) and an oxidizing gas (oxygen gas) are supplied through the oxidizing gas passage 8a and the fuel gas passage 8b. Further, cooling water flows to the cooling water flow path 9 for the purpose of mitigating heat generation at the time of power generation. The cell stack 10 is made up of several hundreds of cells stacked in this order, as shown in Fig.

By supplying an oxidizing gas (oxygen gas) to the fuel gas (hydrogen gas), an oxygen electrode (air electrode) to the fuel electrode, each electrode up the following reaction, overall reaction in which water is produced (H ₂ + 1/2 O ₂ → H ₂ O). More specifically, the protons (H ⁺ ) generated in the anode are diffused in the solid polymer membrane to move toward the oxygen electrode as described below, and water (H ₂ O) generated by the reaction with oxygen is discharged from the oxygen electrode side.

A fuel electrode ^{_{(anode): H 2 → 2H + +}} 2e -

Oxygen electrode (cathode electrode): 1/2 O ₂ + 2H ⁺ + 2e ^- → H ₂ O

In order to start the solid polymer type fuel cell, it is necessary to separately supply the fuel gas containing hydrogen to the anode electrode and the oxidizing gas including oxygen to the cathode electrode separately. If the isolation is insufficient and one gas is mixed with the other gas, the power generation efficiency may be lowered. In this background, a sealing agent is often used for the purpose of preventing leakage of fuel gas, oxygen gas, and the like. Specifically, a sealing agent is used between adjacent separators, between the separator and the frame, between the frame and the electrolyte membrane, or between the MEAs.

The polymer electrolyte membrane is a cation exchange membrane having ion conductivity, and it is preferably a fluoropolymer having a sulfonic acid group since it is chemically stable and strong in operation at a high temperature. Commercially available products include Nafion (registered trademark) of Dupont, Fresion (registered trademark) of Asahi Kasei Corporation, and Asiflex (registered trademark) of Asahi Glass Co., Ltd. Generally, the polymer electrolyte membrane is a material which is difficult to adhere, but can be adhered by using the photo-curable resin composition of the present invention.

Nafion (R)

The fuel electrode is called a hydrogen electrode or an anode, and a known electrode is used. For example, a catalyst in which a catalyst such as platinum, nickel, and ruthenium is supported on carbon is used. Further, the air electrode is referred to as an oxygen electrode or a cathode, and known ones are used. For example, a catalyst in which a catalyst such as platinum and an alloy is supported on carbon is used. The surface of each of the electrodes may be provided with a gas diffusion layer that functions to diffuse a gas or to wet an electrolyte. As the gas diffusion layer, known ones are used, and examples thereof include carbon paper, carbon cloth, carbon fiber and the like.

As shown in Fig. 1, the separator 2 has fine irregular channels, and the fuel gas and the oxidizing gas pass through the separator 2 and are supplied to the electrodes. The separator is made of aluminum, stainless steel, titanium, graphite, carbon, and the like.

The frame is to support and reinforce the thin film electrolyte membrane or MEA so that it does not tear. Examples of the material of the frame include thermoplastic resins such as polyvinyl chloride, polyethylene naphthalate, polyethylene terephthalate, polypropylene and polycarbonate. In order to attach the member using the photo-curable resin composition of the present invention or a cured product thereof, it is preferable that the member is optically transmitted.

The fuel cell of the present invention is a fuel cell characterized by being sealed with the photocurable resin composition of the present invention or a cured product thereof. Examples of the member requiring sealing in the fuel cell include a separator, a frame, an electrolyte, a fuel electrode, an air electrode, and an MEA. More specific sealing positions include between adjacent separators, between the separator and the frame, between the frame and the electrolyte membrane, or between the MEA and the like. The main purpose of sealing between the separator and the frame or between the polymer electrolyte membrane or between the MEA and the frame is to prevent mixing or leakage of the gas and the sealing purpose between the adjacent separators is to prevent leakage of the gas, Thereby preventing the cooling water from leaking to the outside. Further, since the acid generated in the electrolyte membrane causes a strongly acidic atmosphere, the sealant is required to have acid resistance.

<Sealing method>

The sealing method using the photo-curing resin composition of the present invention is not particularly limited, but typically includes FIPG (foam in place gasket), CIPG (cure in place gasket), MIPG (mold in place gasket) .

The FIPG refers to a method in which the photo-curing resin composition of the present invention is applied to a flange of a component to be sealed by an automatic coating apparatus or the like and irradiated with active energy rays such as ultraviolet rays from the flange side And curing the photo-curing resin composition to seal it. More specifically, a method of sealing at least a portion between the at least two flanges in a component to be sealed having at least two flanges, wherein at least one of the flanges is capable of transmitting light of active energy rays, A step of applying the above-mentioned photo-curable resin composition on one surface, a step of attaching one flange coated with the photo-curable resin composition and the other flange through the photo-curing resin composition, And curing the photo-curable resin composition to seal at least a part of the area between the at least two flanges.

CIPG refers to a method of forming a gasket by applying a photo-curable resin composition of the present invention to a flange of a component to be sealed with an automatic coating apparatus or the like and irradiating an active energy ray such as ultraviolet rays to cure the photo-curable resin composition. Then, it is attached to the other flange to perform compression sealing. More specifically, a method of sealing at least a portion between the at least two flanges in a sealed part having at least two flanges, comprising the steps of: applying the above-mentioned photo-curable resin composition to at least one flange of the flange; Curing the photocurable resin composition by irradiating the coated photocurable resin composition with an active energy ray to form a gasket made of a cured product of the photocurable resin composition; placing the other flange on the gasket, And a step of sealing at least a part between the at least two flanges by pressing one flange coated with the chemical composition and the other flange through the gasket.

The MIPG is a method in which a metal mold is pressed against a flange of a pipe to be sealed in advance, a photo-curing resin composition is injected into a hole formed between a mold and a flange of a material capable of transmitting light, Thereby forming a gasket. Then, it is attached to the other flange to perform compression sealing. In addition, the mold is preferably made of a light-transmitting material, and specific examples thereof include glass, polymethylmethacrylate (PMMA), polycarbonate, cycloolefin polymer, and olefin. Further, after the gasket is formed, it is preferable to previously apply a releasing agent such as a fluorine-based resin or a silicon-based resin to the mold in order to facilitate removal from the mold. More specifically, a method for sealing at least a portion between the at least two flanges in a sealed component having at least two flanges, comprising the steps of: disposing a mold for forming a gasket on at least one flange of the flange; Injecting the above-mentioned photo-curable resin composition into at least a part of the air gap between the mold for forming the mold and the flange on which the mold is placed, curing the photo-curable resin composition by irradiating the photo- Forming a gasket made of a cured product of the photo-curable resin composition, separating the mold from the one flange, placing the other flange on the gasket, inserting the one flange and the other flange in the gasket So that at least two of the at least two flanges And a step of sealing a part thereof.

In the liquid injection molding, the photo-curing resin composition of the present invention is poured into a mold of a light-transmittable material at a specific pressure, irradiated with active energy rays such as ultraviolet rays, and photo-cured to form a gasket. Then, it is attached to the other flange to perform compression sealing. The mold is preferably made of a light-transmitting material. Specific examples of the mold include glass, PMMA, polycarbonate, cycloolefin polymer, and olefin. Further, after the formation of the gasket, it is preferable to previously apply a releasing agent such as a fluorine-based resin or a silicon-based resin to the mold for easy separation from the mold.

(Example)

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

The test methods used in Examples and Comparative Examples are as follows.

&Lt; Preparation of photocurable resin composition >

(Example 1)

Each component of Example 1 was taken in the mass parts shown in Table 1 and mixed for 60 minutes at room temperature (25 캜) with a stirrer (apparatus name: Tornado High Power Type PM-202 (manufactured by Asuzon Co., Ltd., revolution: 100 rpm) To prepare a chemical composition, and various physical properties were measured as follows. In addition, the detailed preparation amounts are shown in Table 1, and all values are expressed in parts by mass.

(Examples 2 to 9 and Comparative Examples 1 to 8)

The photocurable resin compositions of Examples 2 to 9 and Comparative Examples 1 to 8 were prepared in the same manner as in Example 1 using the respective components collected in the mass parts shown in Tables 1 and 2, and various physical properties were measured. Further, the detailed preparation amounts were in accordance with Table 1 and Table 2, and all values are expressed in parts by mass.

&Lt; Component (A) >

<a1> Preparation of polyisobutylene polymer (a1) having acryloyloxyethoxyphenyl group

A 5 L separable flask was purged with nitrogen and then 200 mL of n-hexane and 2000 mL of butyl chloride were added and the mixture was cooled to -70 DEG C while stirring under a nitrogen atmosphere. Subsequently, 840 mL (9 mol) of isobutylene, 12 g (0.05 mol) of p-chlorocyclohexyl and 1.1 g (0.012 mol) of 2-methylpyridine were added. After the reaction mixture had cooled to -70 占 폚, 5.0 mL (0.05 mol) of titanium tetrachloride was added to initiate polymerization. After 3 hours from the initiation of polymerization, 40 g of phenoxyethyl acrylate (light acrylate PO-A, manufactured by Kyowa Chemical Co., Ltd.) and 110 mL of titanium tetrachloride were added. Thereafter, stirring was continued at -70 캜 for 4 hours, and then 1000 mL of methanol was added to terminate the reaction.

The supernatant was taken out from the reaction solution, and the solvent and the like were distilled off. The product was dissolved in 3000 mL of n-hexane, washed with 3000 mL of pure water three times, reprecipitated in methanol and then the solvent was distilled off under reduced pressure. Was vacuum-dried at 80 DEG C for 24 hours to obtain a polyisobutylene polymer (a1) having an acryloyloxyethoxyphenyl group.

The a1 includes - [CH ₂ C (CH ₃ ) ₂ ] - units and contains two acryloyl groups. More specifically, a1 is R ¹ in the general formula (1) represents a phenylene group, PIB is polyisobutylene represents a butylene skeleton, R ⁴ are, each represents a hydrocarbon group of a carbon number of ^2, R 2 and R ³ independently Hydrogen atom, R &lt; ⁵ &gt; represents a hydrogen atom, and n is 2.

The average molecular weight (by the chromatographic method, in terms of polystyrene) of the a1 component was 11,100, and the viscosity (25 DEG C) of the a1 component was 1,550 Pa · s.

(3)

&Lt; Component (B) >

b1: benzophenone (reagent)

b2: 2-Hydroxy-2-methyl-1-phenyl-propan-1-one (IRGACURE 1173,

&Lt; Component (C) >

c1: a silicone oligomer (KR-513, manufactured by Shinetsu Kagaku Kogyo Co., Ltd.) having an acryloyl group and a methoxy group in the side chain having an alkoxy group content of 20 wt% and a kinetic viscosity at 25 캜 of 35 mm ² / s,

c2: a silicone oligomer (X-40-2651, manufactured by Shinetsu Kagaku Kogyo Co., Ltd.) having an amino group and a methoxy group in the side chain having an alkoxy group content of 20 wt% and a kinematic viscosity at 25 캜 of 25 mm ² / s,

c3: 3-isocyanate propyltriethoxysilane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.)

&Lt; Comparative component of component (C) >

c'1: a silicone oligomer (X-41-1056, product of Shin-Etsu Chemical Co., Ltd.) having a glycidyl group and a methoxy group having an alkoxy group content of 17 wt% and a kinetic viscosity at 25 캜 of 50 mm ² /

c'2: 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)

c'3: vinyltrimethoxysilane (KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.)

c'4: N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.)

c'5: 3-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.)

&Lt; Component (D) >

d1: dicyclopentanyl methacrylate (FA-513M, manufactured by Hitachi Kasei Co., Ltd.)

The test methods used in Examples and Comparative Examples of Tables 1 and 2 are as follows.

&Lt; Adhesion test for electrolyte membrane >

A photocurable resin composition was applied to a polypropylene (PP) film so as to have a thickness of 50 탆 and attached to a fluoropolymer electrolyte membrane having a sulfonic acid group (Nafion 占 DuPont) to obtain an integrated light quantity of 45 kJ / m &lt; ² &gt; for 20 seconds. Next, in the electrolyte membrane, the cured product of the photo-curing resin composition together with the PP film was peeled off at a rate of 10 mm / min using a tensile tester in the direction of 180 degrees. The adhesion interface was observed, and evaluation was carried out according to the following criteria.

[Evaluation standard]

◎ (excellent): CF (cohesive failure) and membrane break

○ (Good): CF (cohesive failure) and membrane deformation

× (bad): AF (interface breakdown)

According to Examples 1 to 9 of Table 1, it can be seen that the present invention cures rapidly by irradiating active energy rays such as ultraviolet rays (20 seconds) and is excellent in adhesion to an electrolyte membrane which is a material which is difficult to adhere.

In addition, Comparative Example 1 is a composition that does not contain the component (C) of the present invention, but shows poor adhesion to the electrolyte membrane (Table 2). In Comparative Examples 2 to 5, a silicone oligomer having a glycidyl group and a methoxy group other than the component (C) of the present invention, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, N-2- Ethyl) -3-aminopropylmethyldimethoxysilane was used, but adhesion to the electrolyte membrane was poor (Table 2). Comparative Example 8 is a composition in which a silicone oligomer having a glycidyl group and a methoxy group is blended twice as compared with Comparative Example 7, but also has a poor adhesiveness to an electrolyte membrane (Table 2).

(Comparative Example 9)

Comparative Example 9 was prepared in the same manner as in Example 1 except that urethane dimethacrylate having a polybutadiene skeleton (TE-2000, manufactured by Japan Soda Co., Ltd.) was used instead of the component (A) in Example 1 .

(Comparative Example 10)

A comparative example 10 was prepared in the same manner as in Example 2 except that urethane diacrylate having a polyether skeleton (UXF-4002, manufactured by Kayaku KK) was used instead of the component (A) in Example 2 .

<Water vapor permeability (water vapor barrier property)>

The photocurable resin compositions of Examples 1 and 3 and Comparative Examples 9 and 10 were poured into a mold of 200 mm x 200 mm x 0.2 mm. Thereafter, the sheet was irradiated with ultraviolet rays for 20 seconds so as to have an integrated light quantity of 45 kJ / m ² by an ultraviolet irradiator to produce a cured sheet having a thickness of 1.0 mm. 5 g of calcium chloride (anhydrous) was placed in an aluminum cup having an opening of 30 mm in diameter, and the cured product was set in a cup. G / g " was measured, and then the sample was allowed to stand for 24 hours in a constant temperature and humidity bath maintained at a relative humidity of 95% at an atmospheric temperature of 40 DEG C, m ² · 24h) was calculated and evaluated according to the following evaluation criteria. The results are shown in Table 3. Detailed test methods are in accordance with JIS Z 0208. When the water vapor permeability is used as a photo-curable sealant for a fuel cell, it is preferably less than 5 g / m ² · 24 h.

[Evaluation standard]

○ (Good): The moisture permeability is less than 5 g / m ² · 24h

△ (Normal): The moisture permeability is 5 g / m ² · 24 h or more and 50 g / m ² · 24 h or less

× (poor): The moisture permeability is 50 g / m ² · 24 h or more

&Lt; Hydrogen gas barrier property test >

The photo-curable resin compositions of Examples 1 and 3 and Comparative Examples 9 and 10 were measured according to JIS K7126-1: 2006 (Plastic-Film and Sheet-Gas Transmission Test Methods-Part 1: Differential Pressure Method). The test was performed by a pressure sensor method under the following conditions: conditions were 23 deg. C, test gas (hydrogen gas) on the high pressure side was 100 kPa, and sheets were 1 mm thick. The results are shown in Table 3. When the hydrogen gas barrier property is used as a photo-curable seal for a fuel cell, it is preferable that the hydrogen gas barrier property is less than 1 x 10 &lt; ^-15 &gt; m &lt; ² &gt;

[Evaluation standard]

○ ^{(good): 1 × 10 -15 mol ·} m / m 2 · s · Pa under

× (defective): 1 × 10 ^-15 mol · m / m ² · s · Pa or more

According to Examples 1 and 3 of Table 3, it can be seen that the present invention has a low moisture permeability, good hydrogen barrier property, and good sealability. On the other hand, in Comparative Example 9, the urethane dimethacrylate of the polybutadiene skeleton was used in place of the component (A), but the hydrogen gas barrier property was poor. In Comparative Example 10, a urethane diacrylate having a polyether skeleton was used in place of the component (A), and the results showed that the moisture permeability and the hydrogen gas barrier property were inferior.

The photo-curable resin composition of the present invention can be used for various sealing applications because it quickly cures upon irradiation with an active energy ray such as ultraviolet rays and has excellent adhesion to an electrolyte membrane which is a material difficult to adhere. In particular, it is industrially useful because it is effective as a photo-curable sealant for fuel cells.

Another aspect of the present invention may be as follows.

[21]

A photocurable resin composition comprising the following components (A) to (C):

(A): a polymer comprising - [CH ₂ C (CH ₃ ) ₂ ] - units having at least one (meth) acryloyl group

Component (B): photo radical polymerization initiator,

(C): a silicone oligomer having at least one alkoxy group and at least one (meth) acryloyl group, a silicone oligomer each having at least one alkoxy group and at least one amino group, and a silane coupling agent (silane compound) having at least one isocyanate group &Lt; / RTI &gt;

[22]

The photocurable resin composition according to [21], wherein the photocurable resin composition contains a (meth) acrylate monomer as a further component (D).

[23]

The photocurable resin composition according to [22], wherein the component (D) is a (meth) acrylate monomer having an alkyl group having 5 to 30 carbon atoms or an aliphatic cyclic structure.

[24]

The photocurable resin composition according to any one of [21] to [23], wherein the amount of the component (C) is 0.1 to 30 parts by mass based on 100 parts by mass of the component (A).

[25]

The photo-curable resin composition according to any one of [21] to [24], wherein the component (A) is a polyisobutylene polymer represented by the general formula (1).

[Chemical Formula 1]

R ¹ represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic hydrocarbon group. PIB represents a polyisobutylene skeleton. R ⁴ represents a divalent hydrocarbon group which may contain an oxygen atom having 2 to 6 carbon atoms. R ² and R ³ each represent a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms. R ⁵ represents a hydrogen atom, a methyl group, an ethyl group or a propyl group. and n is any one of 1 to 6.

[26]

The silicone oligomer according to any one of [21] to [25], wherein the silicone oligomer having at least one alkoxy group and at least one (meth) acryloyl group as the component (C), the silicone oligomer having at least one alkoxy group and at least one amino group, And a kinematic viscosity at 25 캜 of less than 45 mm ² / s.

[27]

The photocurable resin composition according to any one of [21] to [26], which is used as a sealing agent for a fuel cell.

[28]

The fuel cell according to any one of [21] to [26], which is used as a sealant for a fuel cell peripheral member for any one member selected from the group consisting of a separator, a frame, an electrolyte, a fuel electrode, , A photocurable resin composition.

[29]

The fuel cell as described in any one of [21] to [26], wherein the sealant is a sealant between adjacent separators in the fuel cell, a sealant between the separator and the frame in the fuel cell, a sealant between the fuel cell frame and the electrolyte membrane or MEA Wherein the photocurable resin composition is a photocurable resin composition.

[30]

The photocurable resin composition according to any one of [26] to [28], wherein the fuel cell is a solid polymer type fuel cell.

[31]

The photo-curable resin composition according to any one of the above [21] to [26] is used for sealing between adjacent separators in a fuel cell, sealing between a separator and a frame in a fuel cell, sealing between a frame of the fuel cell and an electrolyte membrane or MEA Wherein the fuel cell is used as a fuel cell.

[32]

The fuel cell according to [30], wherein the fuel cell is a solid polymer type fuel cell.

[33]

The photo-curing resin composition according to any one of the above [21] to [26] is applied to the flange of the component to be sealed, and the active energy ray is irradiated from the side of the light- Characterized in that the resin composition is cured and sealed.

[34]

The photo-curing resin composition according to any one of [21] to [26] above is applied to the flange of the part to be sealed, and the photo-curing resin composition is cured by irradiation with active energy rays to form a gasket, And the sealing member is compressed and sealed.

[35]

A mold is pressed on a flange of a component to be sealed in advance, and a photocurable resin composition of any one of the above-mentioned [21] to [26] is injected into a hole formed between the mold and the flange, And after forming the gasket, sealing with the other flange is performed.

1 Solid polymer fuel cell
2 Separator
3a cathode (cathode)
3b anode (anode)
4 Polymer electrolyte membrane
5 Electrolyte Membrane Electrode Assembly (MEA)
6 frames
7 Adhesive or sealant
8a oxidizing gas flow path
8b fuel gas channel
9 Cooling water flow
10 cell stack
11 Solid polymer fuel cell

Claims (16)

A photocurable resin composition comprising the following components (A) to (C):
(A): a polymer having a polyisobutylene skeleton containing - [CH ₂ C (CH ₃ ) ₂ ] - units having at least one (meth) acryloyl group,
Component (B): Photo radical polymerization initiator
(C): a silicone oligomer having at least one alkoxy group and at least one (meth) acryloyl group, a silicone oligomer each having at least one alkoxy group and at least one amino group, and a silane compound having at least one isocyanate group One or more compounds. The photocurable resin composition according to claim 1, further comprising (meth) acrylate monomer as the component (D). The photocurable resin composition according to claim 2, wherein the component (D) is a (meth) acrylate monomer having an alkyl group having 5 to 30 carbon atoms or an aliphatic cyclic group having 5 to 30 carbon atoms. The photocurable resin composition according to any one of claims 1 to 3, wherein the amount of the component (C) is 0.1 to 30 parts by mass based on 100 parts by mass of the component (A). The photocurable resin composition according to any one of claims 1 to 4, wherein the component (A) is a polymer having a polyisobutylene skeleton represented by the general formula (1).
[Chemical Formula 1]

In the above general formula (1), R ¹ represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic hydrocarbon group, and PIB represents a polyisobutylene containing the - [CH ₂ C (CH ₃ ) ₂ ] butyl represents a butylene skeleton, R ⁴ represents a carbon number of 2 to 62 is a hydrocarbon group that may contain an oxygen atom, R ² and R ³ each independently is 1 a hydrogen atom, a C 1 -C 20 monovalent hydrocarbon group, R ⁵ represents a hydrogen atom, a methyl group, an ethyl group or a propyl group, and n is an integer of 1 to 6; The positive resist composition according to any one of claims 1 to 5, wherein the component (C) is a silicone oligomer having at least one alkoxy group and at least one (meth) acryloyl group, and at least one Silicone oligomer, and the kinematic viscosity (kinematic viscosity) of the silicone oligomer at 25 캜 is less than 45 mm ² / s. A photo-curable sealant for a fuel cell comprising the photo-curable resin composition according to any one of claims 1 to 6. 8. The fuel cell according to claim 7, wherein the photo-curable sealant for fuel cells is a photo-curable sealant for fuel cell peripheral members selected from the group consisting of a separator, a frame, an electrolyte, a fuel electrode, an air electrode and an electrolyte membrane electrode assembly, , Sealant. The fuel cell according to claim 7, wherein the photo-curable sealant for fuel cells is a sealant between adjacent separators in a fuel cell, a sealant between the separator and the frame in the fuel cell, or a sealant between the frame of the fuel cell and the electrolyte membrane or electrolyte membrane electrode assembly Wherein the sealant is a sealant. The sealant according to any one of claims 7 to 9, wherein the fuel cell is a solid polymer type fuel cell. A cured product obtained by photo-curing the photocurable resin composition according to any one of claims 1 to 6. 1. A fuel cell comprising any one of the group consisting of a seal between adjacent separators in a fuel cell, a seal between the separator and the frame in the fuel cell, and a seal between the frame of the fuel cell and the electrolyte membrane or electrolyte membrane electrode assembly, Wherein the one of the seals comprises the cured product according to claim 11. 13. The fuel cell according to claim 12, wherein the fuel cell is a solid polymer type fuel cell. CLAIMS 1. A method for sealing at least a portion between at least two flanges in a component to be sealed having at least two flanges, characterized in that at least one of the flanges is capable of transmitting light of an active energy ray, A step of applying the photocurable resin composition of any one of claims 1 to 6 on the surface, a step of adhering one flange coated with the photocurable resin composition and the other flange through the photocurable resin composition And a step of irradiating an active energy ray through the light-transmitting flange to cure the photo-curing resin composition, thereby sealing at least a part of the at least two flanges. A method of sealing at least a portion between said at least two flanges in a component to be sealed having at least two flanges, characterized in that a photocurable resin composition according to any one of claims 1 to 6 is applied to at least one flange of said flange Curing the photo-curable resin composition by irradiating the applied photo-curable resin composition with an active energy ray to form a gasket made of a cured product of the photo-curable resin composition; And a step of sealing at least a part between the at least two flanges by pressing the one flange coated with the photo-curable resin composition and the other flange through the gasket. Way. A method of sealing at least a portion between at least two flanges in a component to be sealed having at least two flanges, comprising the steps of: disposing a gasket forming mold on at least one flange of the flange; A step of injecting the photo-curable resin composition of any one of claims 1 to 6 into at least a part of the voids between the flanges in which the molds are arranged, irradiating the photo-curable resin composition with the active energy rays, Curing the composition to form a gasket made of a cured product of the photo-curable resin composition; separating the mold from the one flange; placing the other flange on the gasket, The other flange is compressed through the gasket, and the at least two flaps And sealing at least a portion between the land and the land.

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